Fabricating ceramic structures

ABSTRACT

A fabrication apparatus for fabricating ceramic structures of controlled size and composition is provided. The fabrication apparatus includes an additive manufacturing machine configured to dispense preceramic materials in a printed pattern, the printed pattern corresponding to the ceramic structures of the controlled size and composition, a radiation emitter configured to emit curing radiation toward the printed pattern to cure the preceramic materials and a lamp element configured to shine light on the preceramic materials to convert the preceramic materials to ceramics.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. application Ser. No. 16/856,433filed Apr. 23, 2020, the disclosure of which is incorporated herein byreference in its entirety.

BACKGROUND

Exemplary embodiments of the present disclosure relate generally tofabrication methods and, in one embodiment, to fabrication of ceramicstructures.

High-resolution ceramic structures can be used for heat transfer,dielectric functionality, structural enhancement and other applications.Similarly, controlled surface textures, compositions, and feature sizesare often desired to enhance coating performance and adhesion. Existingmethods are typically unable to directly produce such ceramic featureson surfaces, however, and instead require indirect or transfer methodswith ceramic slurries, etching, or vapor deposition.

Accordingly, a need exists for methods of fabricating high-resolutionceramic structures with, in some cases, controlled surface textures.

BRIEF DESCRIPTION

According to an aspect of the disclosure, a fabrication apparatus forfabricating ceramic structures of controlled size and composition isprovided. The fabrication apparatus includes an additive manufacturingmachine configured to dispense preceramic materials in a printedpattern, the printed pattern corresponding to the ceramic structures ofthe controlled size and composition, a radiation emitter configured toemit curing radiation toward the printed pattern to cure the preceramicmaterials and a lamp element configured to shine light on the preceramicmaterials to convert the preceramic materials to ceramics.

In accordance with additional or alternative embodiments, the printedpattern corresponding to the ceramic structures of the controlled sizeand composition has features with sizes on the order of about 100microns or less or about 10 microns or less.

In accordance with additional or alternative embodiments, the printedpattern is dispensed on a substrate and the substrate includes at leastone or more of metallic materials, polymeric materials, carbon-basedmaterials, composite materials, ceramic materials, glass materials andglass/ceramic materials.

In accordance with additional or alternative embodiments, the additivemanufacturing machine includes a heating element to heat the preceramicmaterials and a stage heater to heat a substrate on which the printedpattern is dispensed.

In accordance with additional or alternative embodiments, the additivemanufacturing machine is configured to execute electrohydrodynamic (EHD)deposition.

In accordance with additional or alternative embodiments, the preceramicmaterials include resins with or without fillers, the resins comprisingat least one or more of polysilanes, polysiloxanes, polycarbosilanes,polysilazanes, polycarbosiloxanes, polycarbosilazanes, polyborosiloxanesand metal-modified derivatives and the fillers include at least one ormore of carbides, nitrides, borides, phosphides, carbonitrides, oxides,glasses, glass-ceramics, or metals, including aluminum, copper, silicon,titanium, vanadium, chromium, iron, cobalt, nickel, zinc, hafnium,zirconium, yttrium, lanthanum, ytterbium, gadolinium, niobium, tantalum,boron, tungsten, rhenium, molybdenum, gold, silver, platinum andpalladium.

In accordance with additional or alternative embodiments, the lampelement includes a xenon flash lamp operable to generate intense pulsedlight (IPL) to convert the preceramic materials to ceramics in about 1second or less.

According to an aspect of the disclosure, a method of fabricatingceramic structures of controlled size and composition is provided andincludes printing a pattern of uncured preceramic materials, curing thepattern and converting the preceramic to ceramic.

In accordance with additional or alternative embodiments, the patternincludes features having sizes on the order of about 10 microns or less.

In accordance with additional or alternative embodiments, the preceramicmaterials include resins with or without fillers, the resins comprisingat least one or more of polysilanes, polysiloxanes, polycarbosilanes,polysilazanes, polycarbosiloxanes, polycarbosilazanes, polyborosiloxanesand metal-modified derivatives and the fillers include at least one ormore of carbides, nitrides, borides, phosphides, carbonitrides, oxides,glasses, glass-ceramics, or metals, including aluminum, copper, silicon,titanium, vanadium, chromium, iron, cobalt, nickel, zinc, hafnium,zirconium, yttrium, lanthanum, ytterbium, gadolinium, niobium, tantalum,boron, tungsten, rhenium, molybdenum, gold, silver, platinum andpalladium.

In accordance with additional or alternative embodiments, the methodfurther includes at least one of heating the preceramic and heating thepattern.

In accordance with additional or alternative embodiments, the printingincludes electrohydrodynamic (EHD) deposition.

In accordance with additional or alternative embodiments, the curingincludes exposing the pattern to radiation.

In accordance with additional or alternative embodiments, the convertingincludes intense pulsed light (IPL) processing.

In accordance with additional or alternative embodiments, the methodfurther includes post-processing the ceramic.

In accordance with additional or alternative embodiments, thepost-processing of the ceramic includes applying an additional coating.

According to an aspect of the disclosure, a method of fabricatingceramic structures of controlled size and composition is provided andincludes printing a pattern of uncured preceramic materials withfeatures having sizes on the order of about 10 microns or less,radiating curing radiation toward the pattern to cure the pattern andexposing the cured pattern to intense pulsed light (IPL) to convert thepreceramic of the cured pattern to ceramic.

In accordance with additional or alternative embodiments, the preceramicmaterials include resins with or without fillers, the resins includingat least one or more of polysilanes, polysiloxanes, polycarbosilanes,polysilazanes, polycarbosiloxanes, polycarbosilazanes, polyborosiloxanesand metal-modified derivatives and the fillers including at least one ormore of carbides, nitrides, borides, phosphides, carbonitrides, oxides,glasses, glass-ceramics, or metals, including aluminum, copper, silicon,titanium, vanadium, chromium, iron, cobalt, nickel, zinc, hafnium,zirconium, yttrium, lanthanum, ytterbium, gadolinium, niobium, tantalum,boron, tungsten, rhenium, molybdenum, gold, silver, platinum andpalladium.

In accordance with additional or alternative embodiments, the printingincludes electrohydrodynamic (EHD) deposition.

In accordance with additional or alternative embodiments, the methodfurther includes at least one of heating the preceramic materials andheating the pattern and applying an additional coating to the ceramic.

These and other advantages and features will become more apparent fromthe following description taken in conjunction with the drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

The following descriptions should not be considered limiting in any way.With reference to the accompanying drawings, like elements are numberedalike:

FIG. 1 is a perspective view of an additive manufacturing apparatus forfabricating high-resolution ceramic structures with, in some cases,controlled surface textures in accordance with embodiments;

FIG. 2 is a graphical depiction of a method of fabricatinghigh-resolution ceramic structures with, in some cases, controlledsurface textures in accordance with embodiments; and

FIG. 3 is a flow diagram of a method of fabricating high-resolutionceramic structures with, in some cases, controlled surface textures inaccordance with embodiments.

These and other advantages and features will become more apparent fromthe following description taken in conjunction with the drawings.

DETAILED DESCRIPTION

A detailed description of one or more embodiments of the disclosedapparatus and method are presented herein by way of exemplification andnot limitation with reference to the Figures.

As will be described below, a method is provided to fabricate ceramicstructures of controlled size and composition. The method usesdeliberate combinations of electrohydrodynamic (EHD) jetting, ore-jetting, of preceramic resins/slurries in order to deliver acontrolled pattern and sizes of desired features onto a substrate. Themethod can include optional heating of the substrate before/during/afterdeposition or intense pulsed light (IPL) processing to cure the resinand can be followed by exposure to IPL processing to convert the curedpreceramic features into ceramic structures (i.e., crystalline ceramicstructures in some cases). E-jetting is capable of handling a widevariety of fluids/slurry/compositions and viscosities and printingfeatures below 10 microns onto large area substrates. IPL has beendemonstrated to convert preceramic resins to ceramics in <1 second.

With reference to FIG. 1 , an additive manufacturing machine 101 isprovided and includes a syringe 110 with 0-75 psi back pressurecapability, a syringe holder 111 to support the syringe 110 and adelivery tube 112 at a distal end of the syringe 110. The additivemanufacturing machine 101 further includes a heating element 120, suchas a resistively heated cylinder, through which the delivery tube 112extends as well as a stabilizer 121 to structurally support the heatingelement 120 and delivery tube 112 and a delivery orifice or nozzle 122of the delivery tube 112. The delivery tube 112 can be extended throughthe heating element 120 so that material to be dispensed from the nozzle122 passes through the heating element 120 whereupon the material isheated before being dispensed through the nozzle 122. The dispensing ofthe material through the delivery tube 112 and the nozzle 122 caninvolve EHD jetting, or e-jetting, or other similar processes.

In addition, the additive manufacturing machine 101 includes a stageassembly 130, a radiation emitter 140 (see FIG. 3 ) and a lamp element150 (see FIG. 3 ). The stage assembly 130 includes a substrate support131 with a substrate 1310 on which the delivery tube 122 dispensesmaterial via the nozzle 122 and a stage heater 132 that is configured tomaintain a temperature of material dispensed onto the substrate 1310.The radiation emitter 140 is configured to emit radiation, such asvisible, infrared, ultraviolet, microwave or electron beam curingradiation, onto the material dispensed onto the substrate 1310. Theradiation emitter 140 is configured to provide either continuousradiation or pulses of radiation ranging from microseconds to minutes.The lamp element 150 can include or be provided as a xenon flash lamp151 (see FIG. 3 ) and is configured to expose a printed pattern/featuresto pulsed light, such as IPL.

In accordance with embodiments, the radiation emitter 140 can also beconfigured as a lamp element that is capable of exposing the materialdispensed onto the substrate to pulsed light, such as IPL. In these orother cases, the pulsed light or IPL is used to cure and convert thedispensed material.

The material to be dispensed through the delivery tube 112 and thenozzle 122 can include, but is not limited to, preceramic resins,organometallic compounds, metal-organic compounds, oligomeric materialand slurries including any of these alone or in combinations. Thedispensing pattern can be controlled so as to produce surfaces withdesired features in controlled patterns and sizes. The dispensingpattern can be formed by movement of the delivery tube 112 and thenozzle 122 relative to the stage assembly 130, by movement of the stageassembly 130 relative to the delivery tube 112 and the nozzle 122 orsome combinations of both types of movements. In any case, the relativemovement between the stage assembly 130 and the delivery tube 112 andthe nozzle 122 can be in multiple axes (e.g., 5 or more axes) and withmultiple degrees of freedom.

In accordance with further embodiments, multiple delivery tubes andnozzles, delivering the same or different materials, can also beprovided.

In accordance with embodiments, there can be a voltage drop, potentialdifference, or bias of hundreds to thousand of volts and a separation oftens to hundreds of micrometers between the nozzle 122 and the substrate1310.

In accordance with embodiments, exposures of the printedpattern/features to the pulsed light, such as the IPL, can convertpreceramic materials to ceramics in less than about 1 second. However,it is to be understood that exposure times vary based on the materialsbeing converted, printed layer thickness(es), feature size(s), etc., andthe types, duration and intensities of the radiation to which thosematerials are being exposed, as well as the total exposure times of eachpulse and the pulse-to-pulse frequencies.

In accordance with embodiments, the preceramic resins and the preceramicslurries can include, but are not limited to, at least one or more ofpolysilanes, polysiloxanes, polycarbosilanes, polysilazanes,polycarbosiloxanes, polycarbosilazanes, polyborosiloxanes,metal-modified derivatives, etc., and combinations thereof, and ceramicscan include, but are not limited to, at least one or more of carbides,nitrides, borides, phosphides, carbonitrides, oxides, etc., andcombinations thereof and the substrate 1310 can include, but is notlimited to, at least one or more of metallic materials, polymericmaterials, carbon-based materials, composite materials, ceramicmaterials, glass materials, glass/ceramic materials and combinationsthereof.

The surfaces of the dispensing pattern can have features with sizes onthe order of about 100 microns or less. In some cases, the surfaces ofthe dispensing pattern can have features with sizes on the order ofabout 10 microns or less.

With reference to FIG. 2 , a method of fabricating ceramic structures ofcontrolled size and composition is provided. As shown in FIG. 2 , themethod includes providing a substrate 201 and providing a supply ofuncured preceramic resins, organometallic compounds, metal-organiccompounds, oligomeric material and slurries including any of these aloneor in combinations (e.g., jettable resin/slurry/formulation) 202 andusing the supply of the uncured preceramic resins, organometalliccompounds, metal-organic compounds, oligomeric material and slurriescontaining any of these alone or in combinations to print a pattern ontothe substrate 203 by, for example, electrohydrodynamic (EHD) jetting, ore-jetting, deposition while pre-heating/heating. The method furtherincludes curing the pattern 204 by exposure to radiation or by IPLprocessing, converting the preceramic to ceramic by IPL processing 205and post-processing the ceramic 206 to thereby apply an additionalcoating by, for example, atomic layer deposition (ALD), chemical vapordeposition (CVD), physical vapor deposition (PVD), thermal spraying,slurry spraying, spin coating, etc., or any other similar process.Iterations of operations 203 through 206 are also possible in varioussequences.

It is to be understood that, in some cases, preceramics can be, but arenot necessarily, wholly or partially converted to crystalline materialby IPL processing and there are other cases where preceramics areconverted to ceramics but not necessarily crystalline ceramics. Forthose cases, where whole or partial conversion of preceramics tocrystalline ceramics is desirable, the IPL processing can be designedand executed to complete the conversion to the crystalline state.

Where operations 203-206 are iterative, one might print a pattern andcomplete operations 203-206 and then repeat one or more of operations203-206 in order to achieve either improved structures or to build uponpreviously fabricated patterns in a two+-dimensional (2D or 2.5D)printing method.

As explained above, the pattern can include features having sizes on theorder of about 100 microns or less or, in some cases, on the order ofabout 10 microns or less and the preceramic materials can include resinsand ceramic fillers. The resins can include at least one or more ofpolysilanes, polysiloxanes, polycarbosilanes, polysilazanes,polycarbosiloxanes, polycarbosilazanes, polyborosiloxanes,metal-modified derivatives, etc., and the fillers can include at leastone or more of carbides, nitrides, borides, phosphides, carbonitrides,oxides, glasses, glass-ceramics, or metals, including aluminum, copper,silicon, titanium, vanadium, chromium, iron, cobalt, nickel, zinc,hafnium, zirconium, yttrium, lanthanum, ytterbium, gadolinium, niobium,tantalum, boron, tungsten, rhenium, molybdenum, gold, silver, platinumand palladium.

With reference to FIG. 3 , certain features of the method of FIG. 2 areillustrated. As shown in FIG. 3 , the method includes printing a patternof uncured preceramic materials with features having sizes on the orderof about 10 microns or less 301, radiating curing radiation toward thepattern to cure the pattern 302 and exposing the cured pattern tointense pulsed light (IPL) to wholly or partially convert the preceramicof the cured pattern to ceramic or crystalline ceramic 303. The methodcan further include at least one of heating the preceramic materials andheating the pattern as noted above and applying an additional coating tothe ceramic or crystalline ceramic by ALD, CVD, PVD, thermal spraying,slurry spraying, spin coating, etc. 304.

Benefits of the features described herein are the provision of a highlyversatile manufacturing/printing method that is fast (both e-jetting andIPL processes) and includes an optional coating method, such as atomiclayer deposition, before or after resin conversion for compositional orstructural control. Resins of interest include, but are not limited to,polysilanes, polysiloxanes, polycarbosilanes, polysilazanes,polycarbosiloxanes, polycarbosilazanes, polyborosiloxanes,metal-modified derivatives, etc., and the ceramic fillers can include atleast one or more of carbides, nitrides, borides, phosphides,carbonitrides, oxides, glasses, glass-ceramics, or metals, includingaluminum, copper, silicon, titanium, vanadium, chromium, iron, cobalt,nickel, zinc, hafnium, zirconium, yttrium, lanthanum, ytterbium,gadolinium, niobium, tantalum, boron, tungsten, rhenium, molybdenum,gold, silver, platinum and palladium. The substrates can be metallic,ceramic, glass, etc.

The term “about” is intended to include the degree of error associatedwith measurement of the particular quantity based upon the equipmentavailable at the time of filing the application.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting of the presentdisclosure. As used herein, the singular forms “a”, “an” and “the” areintended to include the plural forms as well, unless the context clearlyindicates otherwise. It will be further understood that the terms“comprises” and/or “comprising,” when used in this specification,specify the presence of stated features, integers, steps, operations,elements, and/or components, but do not preclude the presence oraddition of one or more other features, integers, steps, operations,element components, and/or groups thereof.

While the present disclosure has been described with reference to anexemplary embodiment or embodiments, it will be understood by thoseskilled in the art that various changes may be made and equivalents maybe substituted for elements thereof without departing from the scope ofthe present disclosure. In addition, many modifications may be made toadapt a particular situation or material to the teachings of the presentdisclosure without departing from the essential scope thereof.Therefore, it is intended that the present disclosure not be limited tothe particular embodiment disclosed as the best mode contemplated forcarrying out this present disclosure, but that the present disclosurewill include all embodiments falling within the scope of the claims.

What is claimed is:
 1. A fabrication apparatus for fabricating ceramicstructures of controlled size and composition, the fabrication apparatuscomprising: an additive manufacturing machine configured to dispensepreceramic materials in a printed pattern, the printed patterncorresponding to the ceramic structures of the controlled size andcomposition; a radiation emitter configured to emit curing radiationtoward the printed pattern to cure the preceramic materials; and a lampelement configured to shine light on the preceramic materials to convertthe preceramic materials to ceramics.
 2. The fabrication apparatusaccording to claim 1, wherein the printed pattern corresponding to theceramic structures of the controlled size and composition has featureswith sizes on the order of about 10 microns or less.
 3. The fabricationapparatus according to claim 1, wherein the printed pattern is dispensedon a substrate and the substrate comprises at least one or more ofmetallic materials, polymeric materials, carbon-based materials,composite materials, ceramic materials, glass materials andglass/ceramic materials.
 4. The fabrication apparatus according to claim1, wherein the additive manufacturing machine comprises a heatingelement to heat the preceramic materials and a stage heater to heat asubstrate on which the printed pattern is dispensed.
 5. The fabricationapparatus according to claim 1, wherein the additive manufacturingmachine is configured to execute electrohydrodynamic (EHD) deposition.6. The fabrication apparatus according to claim 1, wherein thepreceramic materials comprise resins with or without fillers, the resinscomprising at least one or more of polysilanes, polysiloxanes,polycarbosilanes, polysilazanes, polycarbosiloxanes, polycarbosilazanes,polyborosiloxanes and metal-modified derivatives and the fillerscomprise at least one or more of carbides, nitrides, borides,phosphides, carbonitrides, oxides, glasses, glass-ceramics, or metals,including aluminum, copper, silicon, titanium, vanadium, chromium, iron,cobalt, nickel, zinc, hafnium, zirconium, yttrium, lanthanum, ytterbium,gadolinium, niobium, tantalum, boron, tungsten, rhenium, molybdenum,gold, silver, platinum and palladium.
 7. The fabrication apparatusaccording to claim 1, wherein the lamp element comprises a xenon flashlamp operable to generate intense pulsed light (IPL) to convert thepreceramic materials to ceramics in about 1 second or less.
 8. Afabrication apparatus for fabricating ceramic structures of controlledsize and composition, the fabrication apparatus comprising: an additivemanufacturing machine configured to execute electrohydrodynamic (EHD)deposition to dispense preceramic materials in a printed pattern, theprinted pattern corresponding to the ceramic structures of thecontrolled size and composition; a radiation emitter configured to emitcuring radiation toward the printed pattern to cure the preceramicmaterials; and a lamp element configured to shine light on thepreceramic materials to convert the preceramic materials to ceramics inabout 1 second or less by intense pulsed light (IPL) processing.
 9. Thefabrication apparatus according to claim 8, wherein the printed patterncorresponding to the ceramic structures of the controlled size andcomposition has features with sizes on the order of about 10 microns orless.
 10. The fabrication apparatus according to claim 8, wherein theprinted pattern is dispensed on a substrate and the substrate comprisesat least one or more of metallic materials, polymeric materials,carbon-based materials, composite materials, ceramic materials, glassmaterials and glass/ceramic materials.
 11. The fabrication apparatusaccording to claim 8, wherein the additive manufacturing machinecomprises a heating element to heat the preceramic materials and a stageheater to heat a substrate on which the printed pattern is dispensed.12. The fabrication apparatus according to claim 8, wherein thepreceramic materials comprise resins with or without fillers, the resinscomprising at least one or more of polysilanes, polysiloxanes,polycarbosilanes, polysilazanes, polycarbosiloxanes, polycarbosilazanes,polyborosiloxanes and metal-modified derivatives and the fillerscomprise at least one or more of carbides, nitrides, borides,phosphides, carbonitrides, oxides, glasses, glass-ceramics, or metals,including aluminum, copper, silicon, titanium, vanadium, chromium, iron,cobalt, nickel, zinc, hafnium, zirconium, yttrium, lanthanum, ytterbium,gadolinium, niobium, tantalum, boron, tungsten, rhenium, molybdenum,gold, silver, platinum and palladium.
 13. The fabrication apparatusaccording to claim 8, wherein the lamp element comprises a xenon flashlamp operable to generate IPL to convert the preceramic materials to theceramics in about 1 second or less.
 14. A fabrication apparatus forfabricating ceramic structures of controlled size and composition, thefabrication apparatus comprising: an additive manufacturing machineconfigured to execute electrohydrodynamic (EHD) deposition to dispensepreceramic materials in a printed pattern, the printed patterncorresponding to the ceramic structures of the controlled size andcomposition; a radiation emitter configured to emit curing radiationtoward the printed pattern to cure the preceramic materials; and a lampelement configured to shine light on the preceramic materials to convertthe preceramic materials to ceramics.
 15. The fabrication apparatusaccording to claim 14, wherein the printed pattern corresponding to theceramic structures of the controlled size and composition has featureswith sizes on the order of about 100 microns or less.
 16. Thefabrication apparatus according to claim 14, wherein the printed patterncorresponding to the ceramic structures of the controlled size andcomposition has features with sizes on the order of about 10 microns orless.
 17. The fabrication apparatus according to claim 14, wherein theprinted pattern is dispensed on a substrate and the substrate comprisesat least one or more of metallic materials, polymeric materials,carbon-based materials, composite materials, ceramic materials, glassmaterials and glass/ceramic materials.
 18. The fabrication apparatusaccording to claim 14, wherein the additive manufacturing machinecomprises a heating element to heat the preceramic materials and a stageheater to heat a substrate on which the printed pattern is dispensed.19. The fabrication apparatus according to claim 14, wherein thepreceramic materials comprise resins with or without fillers, the resinscomprising at least one or more of polysilanes, polysiloxanes,polycarbosilanes, polysilazanes, polycarbosiloxanes, polycarbosilazanes,polyborosiloxanes and metal-modified derivatives and the fillerscomprise at least one or more of carbides, nitrides, borides,phosphides, carbonitrides, oxides, glasses, glass-ceramics, or metals,including aluminum, copper, silicon, titanium, vanadium, chromium, iron,cobalt, nickel, zinc, hafnium, zirconium, yttrium, lanthanum, ytterbium,gadolinium, niobium, tantalum, boron, tungsten, rhenium, molybdenum,gold, silver, platinum and palladium.
 20. The fabrication apparatusaccording to claim 14, wherein the lamp element comprises a xenon flashlamp operable to generate intense pulsed light (IPL) to convert thepreceramic materials to the ceramics in about 1 second or less.